CN113249788B - Fluorinated molybdenum oxyfluoride iodate nonlinear optical crystal material and preparation and application thereof - Google Patents

Fluorinated molybdenum oxyfluoride iodate nonlinear optical crystal material and preparation and application thereof Download PDF

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CN113249788B
CN113249788B CN202110390011.5A CN202110390011A CN113249788B CN 113249788 B CN113249788 B CN 113249788B CN 202110390011 A CN202110390011 A CN 202110390011A CN 113249788 B CN113249788 B CN 113249788B
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张弛
胡艺蕾
吴超
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Tongji University
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Abstract

The invention relates to a fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material and preparation and application thereof, wherein the chemical formula of the nonlinear optical crystal material is AMoO2F3(IO2F2) Wherein a ═ Rb or Cs. Crystal RbMoO of the invention2F3(IO2F2) And CsMoO2F3(IO2F2) Under 1064nm laser irradiation, the powder SHG coefficient is KH2PO45.0 and 4.5 times of (KDP), and can realize phase matching under 1064nm laser irradiation.

Description

Fluorinated molybdenum oxyfluoride iodate nonlinear optical crystal material and preparation and application thereof
Technical Field
The invention belongs to the technical field of nonlinear optical crystals, and relates to a fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material, and preparation and application thereof.
Background
The second-order nonlinear optical crystal is typically characterized by frequency doubling effect (SHG), is an important photoelectric functional material, and has important application prospects in the fields of laser frequency conversion, photoelectric modulation, laser signal holographic storage and the like.
Currently commercialized nonlinear optical materials are BBO (β -barium metaborate), LBO (lithium borate), KDP (potassium dihydrogen phosphate), KTP (potassium titanyl phosphate), and the like. With the development of laser technology and the emergence of tunable lasers, nonlinear optical devices develop rapidly, and laser frequency doubling, frequency mixing, parametric oscillation and amplification are achieved; electro-optical modulation, deflection, Q-switching, and photorefractive devices, etc. occur sequentially. The research and application mentioned above put more and higher requirements on the physical and chemical properties of the nonlinear optical material, and also promote the rapid development of the nonlinear optical material. The second-order nonlinear optical crystal material must have a non-centrosymmetric structure. Recent studies have shown that combining two or more asymmetric polar groups in the same compound is an effective way to induce the synthesis of noncardiac crystals. These asymmetriesThe polar groups include: with flat structural groups having pi-conjugation, e.g. [ BO ]3]3-、[CO3]2-、[NO3]-Etc.; ions containing lone pairs of electrons, such as I (V), Se (IV), Te (IV), Bi (III), Pb (II), etc.; distorted octahedral coordination of d0Electron configuration transition metal ions such as Ti (IV), V (V), Nb (V), Ta (V), Mo (VI), W (VI), etc. With the development of technology and the increase of demand, new nonlinear crystals are continuously developed.
Disclosure of Invention
The invention aims to provide a fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material with a chemical formula of AMoO2F3(IO2F2) Wherein A is Rb or Cs.
Furthermore, the nonlinear optical crystal material belongs to a hexagonal system, and the space group is Cmc21Cell parameter of
Figure BDA0003016286090000021
α＝β＝γ＝90°，Z＝4。
Furthermore, the chemical formula of the nonlinear optical crystal material is RbMoO2F3(IO2F2) Belonging to the orthorhombic system, the space group is Cmc21Cell parameter of
Figure BDA0003016286090000022
Figure BDA0003016286090000023
α＝β＝γ＝90°，Z＝4；
Each asymmetric unit contains 1 Rb, 1 Mo, 1I, 3F and 3O. Each Mo atom forms MoO with 3F atoms and 3O atoms3F3Octahedron. Each I atom is bound to 2O atoms and 2F atoms connected to form IO2F2A polyhedron. MoO3F3Octahedron and IO2F2Polyhedra form zero-dimensional [ MoO ] by sharing one O atom2F3(IO2F2)]2-Building a unit (as in fig. 1 a). [ MoO ]2F3(IO2F2)]2-Building blocks are stacked along the b-axis to form a monolithic three-dimensional structure in which the Rb atoms are located to act as charge balancing (FIG. 1 b).
In particular, the inorganic compound RbMoO2F3(IO2F2) The ultraviolet absorption cut-off wavelength of the crystal is 320-335 nm.
Furthermore, the chemical formula of the nonlinear optical crystal material is CsMoO2F3(IO2F2) Belonging to the orthorhombic system, the space group is Cmc21Cell parameter of
Figure BDA0003016286090000024
Figure BDA0003016286090000025
α＝β＝γ＝90°，Z＝4。
Each asymmetric unit contains 1 Cs, 1 Mo, 1I, 3F and 3O. Each Mo atom forms MoO with 3F atoms and 3O atoms3F3Octahedron. Each I atom is linked to 2O atoms and 2F atoms to form IO2F2A polyhedron. MoO3F3Octahedron and IO2F2Polyhedra form zero-dimensional [ MoO ] by sharing one O atom2F3(IO2F2)]2-Building a unit (as in fig. 1 a). [ MoO ]2F3(IO2F2)]2-The building elements are stacked along the b-axis to form a monolithic three-dimensional structure in which the Cs atoms are located to act as charge balancing (fig. 1 b). Inorganic compound CsMoO2F3(IO2F2) The ultraviolet absorption cut-off wavelength of the crystal is 340-368 nm.
The second technical scheme of the invention provides a preparation method of a fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material, which comprises the steps of mixing an element A source, an element I source, an element Mo source, an element F source and water, placing the mixture in a closed reactor, and carrying out hydrothermal crystallization to obtain a target product.
Furthermore, the addition amounts of the element A source, the element I source, the element Mo source and the element F source meet the following requirements: the molar ratio of the A element, the I element, the Mo element and the F element is 1 (1-10) to 0.5-25 to 1-200. Optionally, the molar ratio of the A element, the I element, the Mo element and the F element is 1 (1-10) to 0.5-25 to 1-100.
Furthermore, the temperature of the hydrothermal crystallization is 180-.
Optionally, the temperature of the hydrothermal crystallization is 210-.
Further, the source of element A is a carbonate of element A; the source I is periodic acid; the Mo source is molybdenum trioxide; the F source is hydrofluoric acid.
Furthermore, when the element A is Rb, the corresponding element A source is rubidium carbonate;
when the element a is Cs, the corresponding source of element a is cesium carbonate.
Further, after crystallization is finished, cooling the system to room temperature at a cooling rate of no more than 15 ℃/h, preferably, the cooling rate is 0.5-13 ℃/h, and further, the cooling rate is 0.5-6 ℃/h.
The third technical scheme of the invention provides application of the fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material in a laser frequency converter.
RbMoO of the invention2F3(IO2F2) The crystal as nonlinear optical crystal material can output strong 532nm green light under 1064nm laser irradiation, and its powder SHG coefficient is KH2PO45.0 times (KDP) and can realize phase matching.
CsMoO of the present invention2F3(IO2F2) The crystal as nonlinear optical crystal material can output strong 532nm green light under 1064nm laser irradiation, and its powder SHG coefficient is KH2PO44.5 times of (KDP) and can realize phaseAnd (4) matching bits.
Compared with the prior art, the invention has the following advantages:
(1) inorganic Compound Crystal RbMoO of the present application2F3(IO2F2) KH is obtained under 1064nm laser irradiation2PO45.0 times (KDP) and can realize phase matching. Thus RbMoO2F3(IO2F2) The crystal has good potential utilization value as a nonlinear optical material.
(2) The inorganic compound crystal RbMoO provided by the application2F3(IO2F2) The material has high transmittance in a spectral range of 335-2500 nm, and the ultraviolet absorption cut-off wavelength is about 328 nm.
(3) The inorganic compound crystal RbMoO provided by the application2F3(IO2F2) And can be stabilized to 276 ℃.
(4) The application also provides the inorganic compound crystal RbMoO2F3(IO2F2) The colorless RbMoO is obtained by the growth of the raw material by a hydrothermal crystallization method2F3(IO2F2) And (4) crystals. The method has simple process, and can obtain the inorganic compound RbMoO with high purity and high crystallinity2F3(IO2F2) A crystalline material.
(5) The application provides a novel inorganic compound crystal CsMoO2F3(IO2F2) KH is obtained under 1064nm laser irradiation2PO44.5 times of (KDP) and can realize phase matching. Thus CsMoO2F3(IO2F2) The crystal has good potential utilization value as a nonlinear optical material.
(6) The inorganic compound crystal CsMoO provided by the application2F3(IO2F2) The material has high transmittance in a spectrum range of 368-2500 nm, and the ultraviolet absorption cut-off wavelength is about 362 nm.
(7) The inorganic compound crystal CsMoO provided by the application2F3(IO2F2) And can be stabilized to 276 ℃.
(8) The application also provides the inorganic compound crystal CsMoO2F3(IO2F2) The colorless CsMoO is obtained by adopting a hydrothermal crystallization method2F3(IO2F2) And (4) crystals. The method has simple process, and can obtain the inorganic compound CsMoO with high purity and high crystallinity2F3(IO2F2) A crystalline material.
Drawings
FIG. 1 is RbMoO2F3(IO2F2) A schematic of the crystal structure of (a); wherein (a) is zero-dimensional [ MoO ]2F3(IO2F2)]2-Constructing a unit schematic diagram; (b) is the projection of the crystal structure onto the bc plane.
FIG. 2 is a comparison of the X-ray diffraction pattern obtained by fitting the crystal structure analyzed by single crystal X-ray diffraction of sample No. 1-1 with the pattern obtained by X-ray diffraction test after sample No. 1-1 is ground into powder.
FIG. 3 is the UV-VIS-NIR absorption spectrum of sample # 1-1.
FIG. 4 is a thermogravimetric analysis plot of sample # 1-1.
FIG. 5 is a graph of the second harmonic signal for sample # 1-1 and a standard KDP sample size in the range of 105-150 μm.
FIG. 6 is a graph showing the phase matching of the second harmonic in the 1064nm band of sample No. 1-1.
FIG. 7 is CsMoO2F3(IO2F2) A schematic of the crystal structure of (a); wherein (a) is zero-dimensional [ MoO ]2F3(IO2F2)]2-Constructing a unit schematic diagram; (b) is the projection of the crystal structure onto the bc plane.
FIG. 8 is a comparison of the X-ray diffraction pattern obtained by fitting the crystal structure analyzed by single crystal X-ray diffraction in sample No. 2-1 with the pattern obtained by X-ray diffraction measurement after sample No. 2-1 was ground into powder.
Fig. 9 is an ultraviolet-visible-near infrared absorption spectrum of sample # 2-1.
FIG. 10 is a thermogravimetric analysis plot of sample # 2-1.
FIG. 11 is a graph of the second harmonic signal for sample # 2-1 and a standard KDP sample size in the range of 105-150 μm.
Fig. 12 is a graph of second harmonic phase matching at the 1064nm band for sample 2-1 #.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the starting products or process techniques, if not specifically mentioned, are all conventional commercial products or conventional processing techniques in the art.
Example 1:
preparation of 1# to 8# samples
Mixing the Rb source, the I source, the Mo source, the F source and water according to a certain proportion to form raw materials, sealing the raw materials in a hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating the raw materials to a crystallization temperature, keeping the temperature for a period of time, slowly cooling the system temperature to room temperature at a certain speed, filtering and cleaning the system temperature to obtain colorless blocky RbMoO2F3(IO2F2) And (4) crystals.
The relationship between the type and ratio of raw materials in the initial mixture, crystallization temperature, crystallization time and sample number is shown in Table 1.
TABLE 1 correspondences between samples and starting materials and Synthesis conditions
Figure BDA0003016286090000051
Analysis of Crystal Structure of 1# -8# sample
And analyzing the structure of the sample 1-1# to 1-8# by adopting a single crystal X-ray diffraction and powder X-ray diffraction method.
Wherein the single crystal X-ray diffraction is carried out on a Bruker company D8 VENTURE CMOS model X-ray single crystal diffractometer. Data receivingMo-Kalpha ray with collection temperature of 293K and monochromatic graphite as diffraction light source
Figure BDA0003016286090000061
Figure BDA0003016286090000062
The scanning mode is omega; the data were subjected to absorption correction processing using the Multi-Scan method. The structure analysis is completed by adopting a SHELXTL-97 program package; determining the position of heavy atom by direct method, and obtaining the coordinates of other atoms by difference Fourier synthesis method; with radicals based on F2The full matrix least square method refines the coordinates and anisotropic thermal parameters of all atoms.
Powder X-ray diffraction was carried out on an X-ray powder diffractometer of the type Bruker D8, Bruker, Germany, under the conditions of a fixed target monochromatic light source Cu-Ka, wavelength
Figure BDA0003016286090000063
The voltage and current are 40kV/20A, the slit DivSlit/RecSlit/SctSlit is 2.00deg/0.3mm/2.00deg respectively, and the scanning range is 5-70°The scanning step size is 0.02 °.
Wherein, the single crystal X-ray diffraction result shows that the samples 1-1# to 1-8# have the same chemical structural formula and crystal structure, and the chemical formula is RbMoO2F3(IO2F2) Belonging to the orthorhombic system, the space group is Cmc21Cell parameter of
Figure BDA0003016286090000064
α＝β＝γ＝90°，Z＝4。
Represented by sample # 1-1, the crystal structure data of which is
Figure BDA0003016286090000065
Figure BDA0003016286090000066
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
Figure BDA0003016286090000067
The crystal structure is shown in figure 1.
Taking the sample 1-1# as a typical representative, as shown in fig. 2, according to the crystal structure analyzed by single crystal X-ray diffraction, the X-ray diffraction pattern obtained by fitting is consistent with the pattern obtained by X-ray diffraction test after the sample 1-1# is ground into powder, and the peak position and the peak intensity are consistent. Indicating that the obtained samples have high purity.
Ultraviolet-visible-near infrared absorption spectrum test
The diffuse reflectance absorption spectrum test of sample # 1 was performed on an agilent company, usa, Carry 5000 type ultraviolet-visible-near infrared spectrophotometer. As shown in FIG. 3, it can be seen from FIG. 3 that the compound does not absorb at 335nm to 2500 nm. The compound has a wide optical transmission range and an optical band gap of 3.77 eV.
Thermogravimetric testing
Thermogravimetric testing of sample # 1 was performed on a thermogravimetric analyzer of the type TGA/DSC1/1100SF of the mettler-toledo international trade (shanghai). The results are shown in FIG. 4, and it can be seen from FIG. 4 that the compound was stable to 276 ℃.
Frequency doubling test experiment and results
The frequency doubling test experiments for samples 1-1# were as follows: YAG solid laser with 1064nm wavelength is used as fundamental frequency light to irradiate the tested crystal powder, the photomultiplier is used to detect the generated second harmonic, and the oscilloscope is used to display the harmonic intensity. Respectively grinding the crystal sample and the KDP crystal of the standard sample, and screening out crystals with different granularities by using a standard sieve, wherein the granularity ranges from less than 26 micrometers, 26-50 micrometers, 50-74 micrometers, 74-105 micrometers, 105-150 micrometers and 150-200 micrometers. And observing the variation trend of the frequency multiplication signal along with the granularity, and judging whether the frequency multiplication signal can realize phase matching. Under the same test condition, the second harmonic intensities generated by the sample and the reference crystal KDP under the 1064nm wavelength laser irradiation are respectively compared, so that the relative magnitude of the frequency doubling effect of the sample is obtained.
The test result shows that the compound RbMoO2F3(IO2F2) The crystal has large frequency doubling effect and can be irradiated by laser with 1064nm wavelengthThe intensity of the frequency doubling signal is 5.0 times that of KDP crystal (see FIG. 5). As shown in FIG. 6, the crystal material can realize phase matching under the 1064nm laser wave band.
Example 2
Preparation of 1# to 8# samples
Mixing a Cs source, an I source, an Mo source, an F source and water according to a certain proportion to form raw materials, sealing the raw materials in a hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating to a crystallization temperature, keeping the temperature for a period of time, slowly cooling the system temperature to room temperature at a certain speed, filtering and cleaning to obtain the colorless block CsMoO2F3(IO2F2) And (4) crystals.
The relationship between the type and ratio of raw materials in the initial mixture, crystallization temperature, crystallization time and sample number is shown in Table 2.
TABLE 2 correspondences between samples and the raw materials employed and the conditions of the synthesis
Figure BDA0003016286090000071
Figure BDA0003016286090000081
Analysis of Crystal Structure of 1# -8# sample
And analyzing the structure of the sample 2-1# to 2-8# by adopting a single crystal X-ray diffraction and powder X-ray diffraction method.
Wherein the single crystal X-ray diffraction is carried out on a Bruker company D8 VENTURE CMOS model X-ray single crystal diffractometer. The data collection temperature is 293K, and the diffraction light source is Mo-Ka ray monochromized by graphite
Figure BDA0003016286090000082
Figure BDA0003016286090000083
The scanning mode is omega; the data were subjected to absorption correction processing using the Multi-Scan method. The structure analysis is completed by adopting a SHELXTL-97 program package; determined by direct methodThe position of the heavy atom, obtain the other atom coordinates with the Fourier synthesis of difference; with radicals based on F2The full matrix least square method refines the coordinates and anisotropic thermal parameters of all atoms.
Powder X-ray diffraction was carried out on an X-ray powder diffractometer of the type Bruker D8, Bruker, Germany, under the conditions of a fixed target monochromatic light source Cu-Ka, wavelength
Figure BDA0003016286090000084
The voltage and current are 40kV/20A, the slit DivSlit/RecSlit/SctSlit is 2.00deg/0.3mm/2.00deg respectively, and the scanning range is 5-70°The scanning step size is 0.02 °.
Wherein, the single crystal X-ray diffraction result shows that the samples 2-1# to 2-8# have the same chemical structural formula and crystal structure, and the chemical formula is CsMoO2F3(IO2F2) Belonging to the orthorhombic system, the space group is Cmc21Cell parameter of
Figure BDA0003016286090000085
α＝β＝γ＝90°，Z＝4。
Represented by sample No. 2-1, the crystal structure data is
Figure BDA0003016286090000086
Figure BDA0003016286090000087
α ═ β ═ γ ═ 90 °, Z ═ 4, and unit cell volume
Figure BDA0003016286090000088
The crystal structure is shown in fig. 7.
Taking the sample 2-1# as a typical representative, as shown in fig. 8, according to the crystal structure analyzed by single crystal X-ray diffraction, the X-ray diffraction pattern obtained by fitting is consistent with the pattern obtained by X-ray diffraction test after the sample 2-1# is ground into powder, and the peak position and the peak intensity are consistent. Indicating that the obtained samples have high purity.
Ultraviolet-visible-near infrared absorption spectrum test
The diffuse reflectance absorption spectrum test of sample # 2-1 was performed on an agilent company, usa, Carry 5000 type ultraviolet-visible-near infrared spectrophotometer. As shown in FIG. 9, it can be seen from FIG. 9 that the compound does not absorb at 368nm to 2500 nm. The compound has a wide optical transmission range and an optical band gap of 3.43 eV.
Thermogravimetric testing
Thermogravimetric testing of sample # 2-1 was performed on a thermogravimetric analyzer of the type TGA/DSC1/1100SF of the mettler-toledo international trade (shanghai). The results are shown in FIG. 10, and it can be seen from FIG. 10 that the compound was stabilized to 276 ℃.
Frequency doubling test experiment and results
The frequency doubling test experiment of sample 2-1# is as follows: YAG solid laser with 1064nm wavelength is used as fundamental frequency light to irradiate the tested crystal powder, the photomultiplier is used to detect the generated second harmonic, and the oscilloscope is used to display the harmonic intensity. Respectively grinding the crystal sample and the KDP crystal of the standard sample, and screening out crystals with different granularities by using a standard sieve, wherein the granularity ranges from less than 26 micrometers, 26-50 micrometers, 50-74 micrometers, 74-105 micrometers, 105-150 micrometers and 150-200 micrometers. And observing the variation trend of the frequency multiplication signal along with the granularity, and judging whether the frequency multiplication signal can realize phase matching. Under the same test condition, the second harmonic intensities generated by the sample and the reference crystal KDP under the 1064nm wavelength laser irradiation are respectively compared, so that the relative magnitude of the frequency doubling effect of the sample is obtained.
The test result shows that the compound CsMoO2F3(IO2F2) The crystal has large frequency doubling effect, and the frequency doubling signal intensity is 4.5 times that of KDP crystal under 1064nm wavelength laser irradiation (as shown in figure 11). As shown in FIG. 12, the crystal material can realize I-type phase matching under the 1064nm laser band.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (9)

1. The fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material is characterized by having a chemical formula of AMoO2F3(IO2F2) Wherein A is Rb or Cs;
the nonlinear optical crystal material belongs to a hexagonal system, and the space group is Cmc21Cell parameter of
Figure FDA0003436980960000011
Figure FDA0003436980960000012
α＝β＝γ＝90°，Z＝4。
2. The fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material as claimed in claim 1, wherein the chemical formula of the nonlinear optical crystal material is RbMoO2F3(IO2F2) Belonging to the orthorhombic system, the space group is Cmc21Cell parameter of
Figure FDA0003436980960000013
Figure FDA0003436980960000014
α＝β＝γ＝90°，Z＝4；
Or the chemical formula of the nonlinear optical crystal material is CsMoO2F3(IO2F2) Belonging to the orthorhombic system, the space group is Cmc21Cell parameter of
Figure FDA0003436980960000015
Figure FDA0003436980960000016
α＝β＝γ＝90°，Z＝4。
3. The method for preparing fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material as claimed in claim 1 or 2, characterized in that the A element source, the I source, the Mo source, the F source and water are mixed and placed in a closed reactor for hydrothermal crystallization to obtain the target product.
4. The method for preparing a fluoromolybdenum oxyfluoride iodate nonlinear optical crystal material as claimed in claim 3, wherein the addition amounts of the element A source, the element I source, the element Mo source and the element F source are as follows: the molar ratio of the A element, the I element, the Mo element and the F element is 1 (1-10) to 0.5-25 to 1-200.
5. The method for preparing fluorinated molybdenum oxyfluoride iodate nonlinear optical crystal material as claimed in claim 3, wherein the temperature of hydrothermal crystallization is 180-250 ℃ and the time is not less than 6 h.
6. The method for preparing fluorinated molybdenum oxyfluoride iodate-based nonlinear optical crystal material as claimed in claim 5, wherein the temperature of hydrothermal crystallization is 210-250 ℃ and the time is 30-120 h.
7. The method for preparing a fluoromolybdenum oxyfluoride iodate-based nonlinear optical crystal material as claimed in claim 3, wherein the A element source is a carbonate of an A element; the source I is periodic acid; the Mo source is molybdenum trioxide; the F source is hydrofluoric acid.
8. The method for preparing a fluoromolybdenum oxyfluoride iodate-based nonlinear optical crystal material as claimed in claim 7, wherein when the element A is Rb, the corresponding element A source is rubidium carbonate;
when the element a is Cs, the corresponding source of element a is cesium carbonate.
9. Use of the fluoromolybdenum oxyfluoride iodate-based nonlinear optical crystal material as claimed in claim 1 or 2 in a laser frequency converter.
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